CN105006381A - Honeycomb nano-double-layer structure super capacitor electrode material and preparation method - Google Patents
Honeycomb nano-double-layer structure super capacitor electrode material and preparation method Download PDFInfo
- Publication number
- CN105006381A CN105006381A CN201510392919.4A CN201510392919A CN105006381A CN 105006381 A CN105006381 A CN 105006381A CN 201510392919 A CN201510392919 A CN 201510392919A CN 105006381 A CN105006381 A CN 105006381A
- Authority
- CN
- China
- Prior art keywords
- electrode material
- super capacitor
- cellular
- preparation
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007772 electrode material Substances 0.000 title claims abstract description 52
- 239000003990 capacitor Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical group [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 52
- 239000010931 gold Substances 0.000 claims abstract description 35
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052737 gold Inorganic materials 0.000 claims abstract description 31
- 238000004070 electrodeposition Methods 0.000 claims abstract description 19
- 238000000151 deposition Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000008021 deposition Effects 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 6
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 6
- 230000001413 cellular effect Effects 0.000 claims description 40
- 239000011572 manganese Substances 0.000 claims description 36
- 239000010409 thin film Substances 0.000 claims description 18
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 241001272567 Hominoidea Species 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 238000009713 electroplating Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 229910017278 MnxOy Inorganic materials 0.000 abstract 3
- 230000005611 electricity Effects 0.000 abstract 2
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 241001466460 Alveolata Species 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to a honeycomb nano-double-layer structure super capacitor electrode material. The lower layer is a multi-hole gold conductive layer. The upper layer is a honeycomb MnxOy oxide layer. The honeycomb diameter of MnxOy oxide is 20-200 nm, the thickness of the hole wall is 10-30 nm, and the thickness of the honeycomb MnxOy oxide layer is 10-200 nm. The invention further provides a preparation method of the electrode material. A multi-hole gold film is loaded on a carrier, the multi-hole gold film serves as a working electrode, an electrodeposition method is utilized in a manganous nitrate and sodium nitrate electrolyte for carrying out deposition of manganese oxide, and the honeycomb nano-double-layer structure super capacitor electrode material is obtained after steps of cleaning and drying. According to the invention, Au good in electricity conductivity is used as a lower layer material to be combined with manganese oxide which is high in specific capacitance and relatively poor in electricity conductivity, so that the obtained super capacitor electrode material is good in structural stability, high in specific capacitance and charging-discharging speed and long in service lifetime.
Description
Technical field
The invention belongs to materialogy field, particularly relate to a kind of electrode material for super capacitor, specifically a kind of cellular nano double-decker electrode material for super capacitor and preparation method thereof.
Background technology
Ultracapacitor is a kind of Novel energy storage apparatus, has charging interval short, the feature such as long service life, energy savings and environmental protection, is widely used in the various fields such as national defence, electric automobile, computer, mobile communication.Ultracapacitor can be divided into double electric layer capacitor and pseudocapacitors according to energy storage mechnism.Compared to double electric layer capacitor, pseudocapacitors has higher ratio capacitance and specific energy.Pseudocapacitors electrode material mainly metal oxide, wherein manganese oxide has higher ratio capacitance (theoretical value 1370 F/g), and cheap, the advantage such as asepsis environment-protecting and rich reserves, become one of focus of super capacitor material research field.But when manganese oxide is as electrode material, because it is semiconductor, therefore conductivity is low, is unfavorable for the electron transmission in redox reaction, limits charge-discharge performance, its high theoretical specific capacity feature is finally caused to be difficult to play.Therefore, electric conducting material must be aided with to make up the shortcoming of its electric conductivity difference.
In order to improve the electric conductivity of manganese oxide, existing process is all the material being mixed into high conductivity in manganese oxide powder, and conventional method is to MnO
2the additives such as graphite (CN103641174A, CN104299787A, CN 201410720452, CN103035417A), active carbon (CN103107024A, CN103413691A, CN104409225A), carbon nano-tube (CN104201006A) and conducting polymer (CN101916667A, CN103854875A, CN103871754A) are added as conductive agent in electrode.But the high conductivity material be mixed into is difficult to be uniformly dispersed in the electrodes, can not form electrons spread passage, the conductance of manganese oxide electrode well can not be improved.Meanwhile, in course of reaction, well can not control the pattern of product, particle size is comparatively large, and there is the problems such as dispersion again of reuniting.
High-performance super capacitor, except the quick transmission of above-mentioned redox reaction, increases the specific surface of electrode material, thus increase electric double layer capacity is another important parameter.For increasing the specific area of electrode material, prior art mainly adopts cluster (CN103077835A), line rod (CN102903532A, CN104599857A, CN104409220A, CN104445422A, CN103762091A), and the structures such as lamella (CN104499022A, CN103641174A, CN102903534A, CN102760583A), tubulose (CN104465123A), nucleocapsid structure (CN104466131A), porous (CN103594253A, CN103332749A) are to improve electrode reaction contact area.But the reaction of manganese oxide fake capacitance mainly betides nearly electrode surface area, and deep regions can not get application, this makes effective bearing capacity of manganese oxide reduce, and significantly limit the raising of its energy density.And these preparation process are complicated.Such as, Chinese invention patent CN104599857A describes a kind of porous graphene/MnO
2the preparation method of pipe coaxial nanowire.First curling graphene film forms grapheme tube, more coated MnO
2nano wire is formed, wherein MnO
2nano wire adds ammonium fluoride by liquor potassic permanganate, after Hydrothermal Synthesis, soaks reduction reaction occurs in hydrazine hydrate.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of cellular nano double-decker electrode material for super capacitor and preparation method thereof, described this cellular nano double-decker electrode material for super capacitor and preparation method thereof solves the technical problem that conductivity is not good, electrode contact area is little of manganese oxide electrode material of the prior art.
The invention provides a kind of cellular nano double-decker electrode material for super capacitor, be made up of double-layer structure, the lower floor of described material is porous gold conductive layer, and upper strata is cellular Mn
xo
yoxide skin(coating), the thickness of described porous gold conductive layer is 80 ~ 120nm, described Mn
xo
ythe honeycomb diameter of oxide between 20 ~ 200nm, pore wall thickness between 10 ~ 30nm, described cellular Mn
xo
ythe thickness of oxide skin(coating) is between 10 ~ 200 nm.
Present invention also offers the preparation method of above-mentioned a kind of cellular nano double-decker electrode material for super capacitor, comprise the steps:
1) by porous gold thin film load thick for 80 ~ 120nm on carrier;
2) using porous gold thin film as work electrode, adopt electro-deposition method in the electro-deposition plating solution containing manganese nitrate and sodium nitrate, carry out the deposition of manganese oxide, voltage is 0.25-2 V, and electroplating time is 10-120 minute, and depositing temperature is 20-80 DEG C;
3) clean, the cellular nano double-decker electrode material for super capacitor that obtains of drying.
Further, in described electro-deposition plating solution, the mass fraction of manganese nitrate is 0.1-5%, and the mass fraction of sodium nitrate is 1.5-2.5%.
Further, in described electro-deposition plating solution, also containing auxiliary agent, the mass fraction of described auxiliary agent is 0.1-2%, described auxiliary agent is the combination of polyethylene glycol, APES, the one or more than one of polypyrrole, softex kw or triethanolamine.
Further, described manganese metal oxide is Mn
3o
4, MnO
2in the combination of one or more than one.
Further, described electro-deposition method is direct current method or impulse method.
Further, also comprise a heat treated step, heat treatment temperature is 100-350 DEG C, and heat treatment time is 20-120 minute.
The present invention utilizes the network structure of porous gold as skeleton, at the honeycomb-shaped oxidizing manganese of its surface deposition.The manganese oxide of deposition is nano-honeycomb mesh network structure, and decentralization is high, abundant with golden substrate contact, forms good conductive network, is beneficial to the transmission of electronics in electrode reaction.Open microporous cellular network, do not reunite between sheet and sheet, honeycomb hole wall thickness is 5-20 nm, and aperture is 50 ~ 200nm, and thickness is 10-200 nm.The honeycomb loose structure that this thin-walled has fine dispersion is conducive to the large effective ratio area of maintenance, is conducive to ion fast transport between electrode and electrolyte, reduce electric charge the evolving path so that the manganese oxide of load can be made full use of, improve stock utilization, thus raising energy density, improve fake capacitance.Be embodied in alveolate texture allow ion through nano-metal-oxide and make it rapid diffusion and transfer nano-metal-oxide and electrolyte, thus carry out quick, reversible redox reaction in electrode material surface, define the structure being similar to pseudocapacitors.The adhesion that electrochemical method prepares this electrode material is comparatively strong, and honeycomb homogeneity is higher, tiny densification, and has the advantages such as preparation condition is simple, mild condition.
The present invention is the manganese oxide covering nanoscale at porous gold thin film surface deposition, adopts electrochemical deposition method, electrochemical deposition manganese oxide in manganese nitrate and sodium nitrate solution, then through washing, vacuumize, can prepare cellular Mn
xo
y@Au nano double Rotating fields electrode material for super capacitor.
Cellular Mn of the present invention
xo
y@Au nano double Rotating fields electrode material, owing to having good electrochemical energy storage ability, high specific capacitance, can be applicable to Nano-function thin films and electrode material for super capacitor technical field, as efficient, low cost combination electrode material.
Cellular Mn of the present invention
xo
y@Au nano double Rotating fields electrode material, electrodeposition process is utilized to prepare nano manganese oxide combination electrode, it can facilitate, control species composition and the parameter such as concentration, temperature of the voltage of electrolytic cell, electrolysis time and electrolyte accurately, thus realizes the control of the index such as quality, thickness, cell size to the manganese oxide electrode film that porous gold surface is formed.
Manganese dioxide is deposited directly on the surface of porous gold thin film by the present invention, effectively raises the conductivity of combination electrode.Morphology controllable of the present invention, technique is simple, easy to operate, reproducible.Because its equipment requirement is low, be conducive to industrialization large-scale production.
The present invention adopts porous gold thin film to be conducting matrix grain, and surface deposition manganese oxide film, improves the conductivity of manganese oxide material.The present invention is in order to adopt cellular nano membrane structure, and open microporous cellular network is diffusion admittance, allows ion to arrive manganese oxide body smoothly, solves the problem that above-mentioned electrode contact area is little.
The present invention compares with prior art, and its technological progress is significant.The present invention using the Au of good conductivity as subsurface material and the Mn oxide that ratio capacitance is high, conductivity is poor combine, prepared Double-layer supercapacitors electrode material has good structural stability, high specific capacitance and charge-discharge velocity and long service life.
Accompanying drawing explanation
Fig. 1 is embodiment 1 gained Mn
3o
4the double-decker SEM of@Au electrode material schemes.
Fig. 2 is embodiment 1 gained Mn
3o
4@Au electrode material surface SEM schemes.
Fig. 3 is embodiment 1 gained Mn
3o
4@Au electrode material cyclic voltammetry curve.
Fig. 4 is embodiment 2 gained MnO
2@Au electrode material surface SEM schemes.
Fig. 5 is embodiment 2 gained MnO
2@Au electrode material cyclic voltammetry curve.
Specific embodiment
Also set forth further the present invention by reference to the accompanying drawings below by specific embodiment, elaboration is below only to explain advantage of the present invention and technical scheme, not limiting the present invention.
embodiment 1
(1) by nanoporous gold thin film thick for 100 nm after distillation moisture film is wetting, be placed on substrate, vacuumize.
(2) using nanoporous gold thin film as work electrode, be placed on containing 0.1% Mn (NO
3)
2solution, 2% NaNO
3in electrolyte, 0.1% polyethylene glycol, carry out the electrochemical deposition of manganese oxide; Deposition voltage 2 V, sedimentation time 30 min, depositing temperature is 23
0c.
(3) cleaning, drying obtain cellular Mn
3o
4@Au nano double Rotating fields electrode material;
Adopt field emission scanning electron microscope to the Mn of above-mentioned gained
3o
4@Au electrode material carries out SEM observation, sees accompanying drawing 1 and accompanying drawing 2.As can be seen from Figure 1, the Mn of gained
3o
4sedimentary deposit grows at nano-porous gold film surface, as shown by arrows in FIG..In accompanying drawing 2, Mn
3o
4oxide is in open microporous cellular network, and do not reunite between sheet and sheet, honeycomb hole wall thickness is 15 nm, and aperture is 150 nm, and thickness is 200 nm.To the Mn of above-mentioned gained
3o
4/ Au puts into 0.5 M Na
2sO
4capacity measurement is carried out, as shown in Figure 3 in solution.At-0.2-0.9 V(vs. SCE) interval, electrode has good capacitance characteristic, and charge/discharge capacity is 417 F/g.
embodiment 2
(1) by nanoporous gold thin film thick for 100 nm after distillation moisture film is wetting, be placed on substrate, vacuumize.
(2) using nanoporous gold thin film as work electrode, 4% Mn (NO is being contained
3)
2solution, 2% NaNO
3in electrolyte, 0.1% polypyrrole, carry out the electrochemical deposition of manganese oxide; Deposition voltage 0.2 V, sedimentation time 10 min, depositing temperature is 80
0c.
(3) cleaning, drying obtain cellular Mn
3o
4@Au nano double Rotating fields electrode material;
(4) by prepared electrode material in 300
0c anneals 120 min, prepares cellular MnO
2@Au nano double Rotating fields electrode material.
Adopt field emission scanning electron microscope to the MnO of above-mentioned gained
2@Au electrode material carries out SEM observation, sees accompanying drawing 4.As can be seen from Figure 4, the MnO of gained
2sedimentary deposit growth is at nano-porous gold film surface, and in open microporous cellular network, honeycomb hole wall thickness is 28 nm, and aperture is 100 nm, and thickness is 100 nm.To the MnO of above-mentioned gained
2@Au puts into 0.5 M Na
2sO
4capacity measurement is carried out, as shown in Figure 5 in solution.At-0.2-0.9 V(vs. SCE) interval, charge/discharge capacity is 598 F/g.
embodiment 3
(1) by nanoporous gold thin film thick for 100 nm after distillation moisture film is wetting, be placed on substrate, vacuumize.
(2) using nanoporous gold thin film as work electrode, 2% Mn (NO is being contained
3)
2solution, 2% NaNO
3in electrolyte, carry out the electrochemical deposition of manganese oxide; Employing pulse voltage deposits, and voltage 0.8 V, sedimentation time 10 min, depositing temperature is 20
0c.
(3) cleaning, drying obtain cellular Mn
3o
4@Au nano double Rotating fields electrode material;
The Mn of gained
3o
4sedimentary deposit growth is at nano-porous gold film surface, and in open microporous cellular network, honeycomb hole wall thickness is 10 nm, and aperture is 20 nm, and thickness is 10 nm.To the Mn of above-mentioned gained
3o
4/ Au puts into 0.5 M Na
2sO
4capacity measurement is carried out, at-0.2 ~ 0.9 V(vs in solution. SCE) interval, charge/discharge capacity is 246 F/g.
embodiment 4
(1) by nanoporous gold thin film thick for 100 nm after distillation moisture film is wetting, be placed on substrate, vacuumize.
(2) using nanoporous gold thin film as work electrode, 0.5% Mn (NO is being contained
3)
2solution, 2% NaNO
3in electrolyte, carry out the electrochemical deposition of manganese oxide; Adopt constant voltage deposition, voltage 0.9 V, sedimentation time 60 min, depositing temperature is 40
0c.
(3) cleaning, drying obtain cellular Mn
3o
4@Au nano double Rotating fields electrode material;
(4) cellular electrode material will be obtained in 100
0c anneals 20 min, prepares cellular MnO
2/ Mn
3o
4@Au nano double Rotating fields electrode material.
The MnO of gained
2/ Mn
3o
4sedimentary deposit growth is at nano-porous gold film surface, and in open microporous cellular network, honeycomb hole wall thickness is 20 nm, and aperture is 100 nm.To the MnO of above-mentioned gained
2/ Mn
3o
4@Au puts into 0.5 M Na
2sO
4capacity measurement is carried out, at-0.2 ~ 0.9 V(vs in solution. SCE) interval, charge/discharge capacity is 476 F/g.
embodiment 5
(1) by nanoporous gold thin film thick for 80 nm after distillation moisture film is wetting, be placed on substrate, vacuumize.
(2) using nanoporous gold thin film as work electrode, 0.5% Mn (NO is being contained
3)
2solution, 2.5% NaNO
3, in 2% softex kw electrolyte, carry out the electrochemical deposition of manganese oxide; Adopt constant voltage deposition, voltage 1.5 V, sedimentation time 120 min, depositing temperature is 23
0c.
(3) cleaning, drying obtain cellular Mn
3o
4@Au nano double Rotating fields electrode material;
(4) cellular electrode material will be obtained in 350
0c anneals 120 min, prepares cellular MnO
2@Au nano double Rotating fields electrode material.
The MnO of gained
2/ Mn
3o
4sedimentary deposit growth is at nano-porous gold film surface, and in open microporous cellular network, honeycomb hole wall thickness is 30 nm, and aperture is 200 nm, thickness 200nm.To the MnO of above-mentioned gained
2@Au puts into 0.5 M Na
2sO
4capacity measurement is carried out, at-0.2 ~ 0.9 V(vs in solution. SCE) interval, charge/discharge capacity is 575 F/g.
Foregoing be only the present invention conceive under basic explanation, and according to any equivalent transformation that technical scheme of the present invention is done, all should protection scope of the present invention be belonged to.
Claims (7)
1. a cellular nano double-decker electrode material for super capacitor, is characterized in that: the lower floor of described material is porous gold conductive layer, and upper strata is cellular Mn
xo
yoxide skin(coating), the thickness of described porous gold conductive layer is 80 ~ 120nm, described Mn
xo
ythe honeycomb diameter of oxide between 20 ~ 200nm, pore wall thickness between 10 ~ 30nm, described cellular Mn
xo
ythe thickness of oxide skin(coating) is between 10 ~ 200 nm.
2. the preparation method of a kind of cellular nano double-decker electrode material for super capacitor according to claim 1, is characterized in that comprising the steps:
By porous gold thin film load thick for 80 ~ 120nm on carrier;
Using porous gold thin film as work electrode, adopt electro-deposition method in the electro-deposition plating solution containing manganese nitrate and sodium nitrate, carry out the deposition of manganese oxide, voltage is 0.25-2 V, and electroplating time is 10-120 minute, and depositing temperature is 20-80 DEG C;
Cleaning, drying obtain cellular nano double-decker electrode material for super capacitor.
3. the preparation method of a kind of cellular nano double-decker electrode material for super capacitor according to claim 2, is characterized in that: in described electro-deposition plating solution, and the mass fraction of manganese nitrate is 0.1-5%, and the mass fraction of sodium nitrate is 1.5-2.5%.
4. the preparation method of a kind of cellular nano double-decker electrode material for super capacitor according to claim 3, it is characterized in that: in described electro-deposition plating solution, also containing auxiliary agent, the mass fraction of described auxiliary agent is 0.1-2%, described auxiliary agent is the combination of polyethylene glycol, APES, the one or more than one of polypyrrole, softex kw or triethanolamine.
5. the preparation method of a kind of cellular nano double-decker electrode material for super capacitor according to claim 2, is characterized in that: described manganese metal oxide is Mn
3o
4, MnO
2in the combination of one or more than one.
6. the preparation method of a kind of cellular nano double-decker electrode material for super capacitor according to claim 2, is characterized in that: described electro-deposition method is direct current method or impulse method.
7. the preparation method of a kind of cellular nano double-decker electrode material for super capacitor according to claim 2, it is characterized in that: also comprise a heat treated step, heat treatment temperature is 100-350 DEG C, and heat treatment time is 20-120 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510392919.4A CN105006381A (en) | 2015-07-07 | 2015-07-07 | Honeycomb nano-double-layer structure super capacitor electrode material and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510392919.4A CN105006381A (en) | 2015-07-07 | 2015-07-07 | Honeycomb nano-double-layer structure super capacitor electrode material and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105006381A true CN105006381A (en) | 2015-10-28 |
Family
ID=54379013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510392919.4A Pending CN105006381A (en) | 2015-07-07 | 2015-07-07 | Honeycomb nano-double-layer structure super capacitor electrode material and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105006381A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106910637A (en) * | 2017-02-28 | 2017-06-30 | 广东工业大学 | A kind of combination electrode material and preparation method thereof and ultracapacitor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103270565A (en) * | 2010-12-21 | 2013-08-28 | 国立大学法人东北大学 | Nanoporous ceramic composite metal |
| CN103346027A (en) * | 2013-07-08 | 2013-10-09 | 山东大学 | Supercapacitor material manufacturing technology based on nano-porous titanium skeleton |
| CN103956274A (en) * | 2014-04-22 | 2014-07-30 | 上海大学 | Super capacitor combined electrode preparing method |
-
2015
- 2015-07-07 CN CN201510392919.4A patent/CN105006381A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103270565A (en) * | 2010-12-21 | 2013-08-28 | 国立大学法人东北大学 | Nanoporous ceramic composite metal |
| CN103346027A (en) * | 2013-07-08 | 2013-10-09 | 山东大学 | Supercapacitor material manufacturing technology based on nano-porous titanium skeleton |
| CN103956274A (en) * | 2014-04-22 | 2014-07-30 | 上海大学 | Super capacitor combined electrode preparing method |
Non-Patent Citations (2)
| Title |
|---|
| JIANLI KANG等: "Electroplated Thick Manganese Oxide Films with Ultrahigh Capacitance", 《ADVANCED ENERGY MATERIALS》 * |
| L. Y. CHEN等: "High-energy-density nonaqueous MnO2@nanoporous gold based supercapacitors", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106910637A (en) * | 2017-02-28 | 2017-06-30 | 广东工业大学 | A kind of combination electrode material and preparation method thereof and ultracapacitor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lo et al. | Synthesis of Ni (OH) 2 nanoflakes on ZnO nanowires by pulse electrodeposition for high-performance supercapacitors | |
| EP2613389B1 (en) | Lithium air battery | |
| Jin et al. | Electrochemical properties of α-Co (OH) 2/graphene nano-flake thin film for use as a hybrid supercapacitor | |
| CN102709058B (en) | Method for preparing manganese dioxide-nickel hydroxide composite electrode materials of super capacitors | |
| CN106898778A (en) | A kind of metal secondary batteries negative pole three-dimensional collector and its production and use | |
| CN105513831A (en) | Electrode material in hollow tubular structure, and preparation method for electrode material | |
| Yin et al. | A nickel foam supported copper core/nickel oxide shell composite for supercapacitor applications | |
| CN102664107B (en) | Preparation method of nano-manganese dioxide electrode | |
| US20100126870A1 (en) | Controlled electrodeposition of nanoparticles | |
| CN106910637A (en) | A kind of combination electrode material and preparation method thereof and ultracapacitor | |
| CN102013330A (en) | Film for graphene/porous nickel oxide composite super capacitor and preparation method thereof | |
| Yang et al. | Rationally designed hierarchical MnO2-shell/ZnO-nanowire/carbon-fabric for high-performance supercapacitor electrodes | |
| CN104409222A (en) | Preparation method for ternary composites of graphene/manganese dioxide nanosheet /polyaniline nanorod | |
| CN108899222B (en) | Preparation method of supercapacitor electrode material | |
| Zhou et al. | High areal capacitance three-dimensional Ni@ Ni (OH) 2 foams via in situ oxidizing Ni foams in mild aqueous solution | |
| CN110335759A (en) | Load nickel hydroxide nano piece and the nanocrystalline carbon nano-fiber composite material and its preparation method and application of cobalt acid nickel | |
| CN105948132B (en) | Preparation method of three-dimensional gamma-Fe2O3 nano material and application thereof | |
| CN112382513B (en) | Preparation method of double-ion water system energy storage device | |
| CN107045945A (en) | A kind of super capacitor anode based on conductive substrates direct growth nitrogen-doped carbon cobalt compound microplate array and preparation method thereof | |
| CN105448536B (en) | Nickel oxide/TiOx nano composite material and preparation method thereof and stored energy application | |
| CN106024414A (en) | Manganese dioxide/polypyrrole composite electrode free of binder, preparation method and application of manganese dioxide/polypyrrole composite electrode | |
| CN103606683A (en) | Coiling-type germanium nanomaterial and preparation method thereof | |
| CN108461301B (en) | MnO (MnO)2-PPy/H-TiO2Ternary core-shell hybrid array electrode material and preparation method thereof | |
| KR20130140946A (en) | Method for manufacturing graphite film electro-deposited metal oxide for supercapacitor electrode and supercapacitor comprising the same | |
| CN110942923B (en) | Preparation method of carbon cloth in-situ growth sandwich type core-shell electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20151028 |
|
| WD01 | Invention patent application deemed withdrawn after publication |